Photographic color developer compositions

Abstract

An hydroxylamine and a member selected from the group consisting of alkanolamines which are free of carboxyl substitution, aliphatic monoamino monocarboxylic acids of up to three carbon atoms, and aminobenzoic acids, are employed in combination in a photographic color developing composition comprising a primary aromatic amino color developing agent for the purpose of retarding aerial oxidation of the developing agent. This combination can be used to replace all or part of the sulfite that is commonly employed in color developers, to thereby avoid or reduce the disadvantages resulting from the fact that sulfite competes with couplers for oxidized developing agent.

What is claimed is: 
     
       1. A photographic color developing composition comprising (1) a primary aromatic amino color developing agent, (2) an hydroxylamine and (3) a member selected from the group consisting of (a) alkanolamines which are free of carboxyl substitution, and are represented by the formula ##STR6## wherein R 1  is an hydroxyalkyl group of 2 to 6 carbon atoms and each of R 2  and R 3  is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an hydroxyalkyl group of 2 to 6 carbon atoms, a benzyl radical, or a ##STR7## wherein n is an integer of from 1 to 6 and each of X and Y is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms or an hydroxyalkyl group of 2 to 6 carbon atoms, (b) aliphatic monoamino monocarboxylic acids of up to 3 carbon atoms, and (c) aminobenzoic acids; the concentration of (2) and (3) being sufficient to retard aerial oxidation of said primary aromatic amino color developing agent. 
     
     
       2. A photographic color developing composition comprising a primary aromatic amino color developing agent and a concentration sufficient to retard aerial oxidation of said developing agent of a combination of an hydroxylamine with an alkanolamine which is free of carboxyl substitution and is represented by the formula ##STR8## wherein R 1  is an hydroxyalkyl group of 2 to 6 carbon atoms and each of R 2  and R 3  is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an hydroxyalkyl group of 2 to 6 carbon atoms, a benzyl radical, or a ##STR9## wherein n is an integer of from 1 to 6 and each of X and Y is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms or an hydroxyalkyl group of 2 to 6 carbon atoms. 
     
     
       3. A photographic color developing composition as claimed in claim 2 wherein said alkanolamine is a secondary monoamine, a tertiary monoamine, a secondary diamine or a tertiary diamine. 
     
     
       4. A photographic color developing composition comprising a primary aromatic amino color developing agent and a concentration sufficient to retard aerial oxidation of said developing agent of a combination of an hydroxylamine with an aliphatic monoamino monocarboxylic acid of up to 3 carbon atoms. 
     
     
       5. A photographic color developing composition comprising a primary aromatic amino color developing agent and a concentration sufficient to retard aerial oxidation of said developing agent of a combination of an hydroxylamine with an aminobenzoic acid. 
     
     
       6. A photographic color developing composition comprising (1) a primary aromatic amino color developing agent, (2) an hydroxylamine of the formula ##STR10## wherein R is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, or a water-soluble acid salt thereof, and (3) a member selected from the group consisting of (a) alkanolamines which are free of carboxyl substitution and are represented by the formula ##STR11## wherein R 1  is an hydroxyalkyl group of 2 to 6 carbon atoms and each of R 2  and R 3  is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an hydroxyalkyl group of 2 to 6 carbon atoms, a benzyl radical, or a ##STR12## wherein n is an integer of from 1 to 6 and each of X and Y is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms or an hydroxyalkyl group of 2 to 6 carbon atoms, (b) aliphatic monoamino monocarboxylic acids of up to 3 carbon atoms, and (c) aminobenzoic acids; the concentration of (2) and (3) being sufficient to retard aerial oxidation of said primary aromatic amino color developing agent. 
     
     
       7. A photographic color developing composition comprising (1) a primary aromatic amino color developing agent, (2) from about 1 to about 8 moles per mole of said developing agent of an hydroxylamine of the formula ##STR13## wherein R is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, or a water-soluble acid salt thereof, and (3) from about 4 to about 30 moles per mole of said developing agent of an alkanolamine which is free of carboxyl substitution and is represented by the formula ##STR14## wherein R 4  is an hydroxyalkyl group of 2 to 4 carbon atoms and each of R 5  and R 6  is an alkyl group of 1 to 4 carbon atoms or an hydroxyalkyl group of 2 to 4 carbon atoms. 
     
     
       8. A photographic color developing composition comprising (1) a primary aromatic amino color developing agent, (2) from about 1 to about 8 moles per mole of said developing agent of an hydroxylamine of the formula ##STR15## wherein R is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, or a water-soluble acid salt thereof, (3) from about 4 to about 30 moles per mole of said developing agent of a member selected from the group consisting of (a) alkanolamines which are free of carboxyl substitution and are represented by the formula ##STR16## wherein R 1  is an hydroxyalkyl group of 2 to 6 carbon atoms and each of R 2  and R 3  is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an hydroxyalkyl group of 2 to 6 carbon atoms, a benzyl radical, or a ##STR17## wherein n is an integer of from 1 to 6 and each of X and Y is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, or an hydroxyalkyl group of 2 to 6 carbon atoms, (b) aliphatic monoamino monocarboxylic acids of up to 3 carbon atoms, and (c) aminobenzoic acids, and (4) from zero to 0.2 moles of sulfite per mole of said developing agent. 
     
     
       9. A photographic color developing composition as claimed in claim 1 wherein said developing agent is a p-phenylenediamine. 
     
     
       10. A photographic color developing composition as claimed in claim 1 wherein said developing agent is an aminophenol. 
     
     
       11. A photographic color developing composition as claimed in claim 1 wherein said developing agent is 4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate. 
     
     
       12. A photographic color developing composition as claimed in claim 1 wherein said composition additionally contains benzyl alcohol. 
     
     
       13. A photographic color developing composition as claimed in claim 1 which is free of sulfite ions. 
     
     
       14. A photographic color developing composition as claimed in claim 1 wherein (2) is hydroxylamine sulfate and (3) is triethanolamine. 
     
     
       15. A photographic color developing composition as claimed in claim 1 wherein (2) is hydroxylamine sulfate and (3) is diethanolamine. 
     
     
       16. A photographic color developing composition as claimed in claim 1 wherein (2) is hydroxylamine sulfate and (3) is glycine. 
     
     
       17. A photographic color developing composition as claimed in claim 1 wherein (2) is hydroxylamine sulfate and (3) is 2-dimethylaminoethanol. 
     
     
       18. A photographic color developing composition as claimed in claim 1 wherein (2) is hydroxylamine sulfate and (3) is ortho-aminobenzoic acid. 
     
     
       19. A photographic color developing composition containing 4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate, benzyl alcohol, hydroxylamine sulfate and triethanolamine; said composition being free of sulfite ions and containing a sufficient concentration of said hydroxylamine sulfate and said triethanolamine to retard aerial oxidation of said 4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate. 
     
     
       20. A method of retarding aerial oxidation of a primary aromatic amino color developing agent in a photographic color developing solution so as to increase the useful life of said solution, which method comprises incorporating in said solution a combination of an hydroxylamine with a member selected from the group consisting of (a) alkanolamines which are free of carboxyl substitution, and are represented by the formula ##STR18## wherein R 1  is an hydroxyalkyl group of 2 to 6 carbon atoms and each of R 2  and R 3  is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an hydroxyalkyl group of 2 to 6 carbon atoms, a benzyl radical, or a ##STR19## wherein n is an integer of from 1 to 6 and each of X and Y is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, or an hydroxyalkyl group of 2 to 6 carbon atoms, (b) aliphatic monoamino monocarboxylic acids of up to 3 carbon atoms, and (c) aminobenzoic acids, the concentration of said combination being sufficient to retard aerial oxidation of said developing agent. 
     
     
       21. A method as claimed in claim 20 wherein said hydroxylamine is a compound of the formula ##STR20## wherein R is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, or a water-soluble acid salt thereof. 
     
     
       22. A method as claimed in claim 20 wherein said alkanolamine has the formula: ##STR21## wherein R 4  is an hydroxyalkyl group of 2 to 4 carbon atoms and each of R 5  and R 6  is an alkyl group of 1 to 4 carbon atoms or an hydroxyalkyl group of 2 to 4 carbon atoms. 
     
     
       23. A method as claimed in claim 20 wherein said hydroxylamine is hydroxylamine sulfate. 
     
     
       24. A method as claimed in claim 20 wherein said alkanolamine is triethanolamine. 
     
     
       25. A method as claimed in claim 20 wherein said alkanolamine is diethanolamine. 
     
     
       26. A method as claimed in claim 20 wherein said alkanolamine is 2-dimethylaminoethanol. 
     
     
       27. A method as claimed in claim 20 wherein said aliphatic monoamino monocarboxylic acid is glycine. 
     
     
       28. A method as claimed in claim 20 wherein said aminobenzoic acid is ortho-aminobenzoic acid. 
     
     
       29. A method as claimed in claim 20 wherein said developing agent is 4-amino-N-ethyl-N-(β-methane-sulfonamidoethyl)-m-toluidine sesquisulfate monohydrate. 
     
     
       30. A process of color developing a photographic element which comprises contacting said element with a color developing composition containing a primary aromatic amino color developing agent stabilized against aerial oxidation with a combination of (1) an hydroxylamine and (2) a member selected from the group consisting of (a) alkanolamines which are free of carboxyl substitution, and are represented by the formula ##STR22## wherein R 1  is an hydroxyalkyl group of 2 to 6 carbon atoms and each of R 2  and R 3  is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an hydroxyalkyl group of 2 to 6 carbon atoms, a benzyl radical, or a ##STR23## wherein n is an integer of from 1 to 6 and each of X and Y is a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, or an hydroxyalkyl group of 2 to 6 carbon atoms, (b) aliphatic monoamino monocarboxylic acids of up to 3 carbon atoms, and (c) aminobenzoic acids. 
     
     
       31. A process as claimed in claim 30 wherein said hydroxylamine is a compound of the formula ##STR24## wherein R is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, or a water-soluble acid salt thereof. 
     
     
       32. A process as claimed in claim 30 wherein said alkanolamine has the formula: ##STR25## wherein R 4  is an hydroxyalkyl group of 2 to 4 carbon atoms and each of R 5  and R 6  is an alkyl group of 1 to 4 carbon atoms, or an hydroxyalkyl group of 2 to 4 carbon atoms. 
     
     
       33. A process as claimed in claim 30 wherein said hydroxylamine is hydroxylamine sulfate. 
     
     
       34. A process as claimed in claim 30 wherein said alkanolamine is triethanolamine. 
     
     
       35. A process as claimed in claim 30 wherein said alkanolamine is diethanolamine. 
     
     
       36. A process as claimed in claim 30 wherein said alkanolamine is 2-dimethylaminoethanol. 
     
     
       37. A process as claimed in claim 30 wherein said aliphatic monoamino monocarboxylic acid is glycine. 
     
     
       38. A process as claimed in claim 30 wherein said aminobenzoic acid is ortho-aminobenzoic acid. 
     
     
       39. A process as claimed in claim 30 wherein said developing agent is 4-amino-N-ethyl-N-(β-methane-sulfonamidoethyl)-m-toluidine sesquisulfate monohydrate.